Enhancing or augmenting the aroma of detergents using 4-methyl-3-cyclohexene-1-carboxylic

ABSTRACT

Described in the compound, 4-methyl-3-cyclohexene-1-carboxylic acid having the structure: ##STR1## and the use thereof in augmenting or enhancing the aroma of perfume compositions, perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions and fabric softener articles as well as bath preparations and hair preparations). The said 4-methyl-3-cyclohexene-1-carboxylic acid is particularly useful as a replacement for cumin oil and/or cumin aldehyde in perfume compositions, colognes and perfumed articles.

This is a divisional of application Ser. No. 299,211, filed Sept. 3,1981.

BACKGROUND OF THE INVENTION

The instant invention relates to the use in perfumery and particularlyin augmenting or enhancing the aroma of perfume compositions, colognesand perfumed articles of the compound,4-methyl-3-cyclohexene-1-carboxylic acid having the structure: ##STR2##particularly to replace in perfume compositions cumin oil or cuminaldehyde.

As a general rule, cumin oil is used in perfume compositions in traceamounts to introduce green-spicy and green-woody top notes particularlyin the woody, floral perfumed types, Oriental bases, mimosa, cassie, andviolet. It is also used for "special effects" in modern aldehydicfragrances and for its unusual diffusive power. The oil blends well withlavandin, rosemary, galbanum, oakmoss, bois de rose and the like and itperforms well in soaps although it may discolor a white soap tabletvisibly after a few months of aging. Cuminaldehyde(p-isopropylbenzaldehyde) occurs to the extent of about 30% in cumin oiland has also been found in traces in the oils of cassie flowers,cinnamon, myrrh and boldo leaf. Its odor recalls orris and it is knownin the perfume industry to be useful in preparing synthetic cassie,orris, foin coupe, lilac, lily, mimosa and violet perfumes.

Unfortunately, both cumin oil and cumin aldehyde as well as otherconstituents of cumin oil, e.g., cymene have been found to cause aconsiderable degree of irritation to certain perfume wearers in certainclimates. Accordingly, a need has arisen for:

(i) A synthetic replacement for cumin oil and/or cumin aldehyde whichhas no irritency effect in any climate and;

(ii) A replacement for cumin oil which will not discolor soaps.

The use in perfumery of cyclohexene carboxylic acid derivatives is wellknown. Thus, U.S. Pat. No. 4,113,663 discloses2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester of theformula: ##STR3## It is indicated in U.S. Pat. No. 4,113,663 that thiscompound has a particular odor and properties providing an extremelydiffuse rose note of very remarkable radiance which is accompanied byhoney like, warm and spicy,fruity,berry like side notes. It is furtherindicated that the woody, lightly flowery base note with fruity berrylike side notes is reminiscent of dried fruits. Disclosed is theintermediate for preparing this ester, the carboxylic acid having thestructure: ##STR4##

Also described in U.S. Pat. No. 4,113,663 are the following cyclohexenecarboxylic acid esters and their organoleptic properties:

    __________________________________________________________________________     ##STR5##    camphorous, woody, very dry, flat, medicinal side-note                                   ##STR6##    woody, dry, tangy, slightly sweet;         ##STR7##    camphorous, woody, and weak                                                          and                                                                               ##STR8##    agreste, [rustic] [reminiscent of                                             eucalyptus seeds], slightly woody and                                         eppery-spicy, some- what fruity,                                              similar to tobacco.                       __________________________________________________________________________

No mention is made in U.S. Pat. No. 4,113,663 of replacement bycyclohexene carboxylic acids of cumin oil or cumin aldehyde.

There has also been determined in the perfume industry to be a need forperfume nuance combinations of cedar like notes with cumin like notesand further with "sweaty" and "leathery" notes.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the reaction product of Example Icontaining the compound having the structure: ##STR9##

FIG. 2 is the IR spectrum for the reaction product of Example Iconsisting of the compound having the structure: ##STR10##

THE INVENTION

The present invention provides the compound having the structure:##STR11## which can exist into forms "endo" having the structure:##STR12## and "exo" having the structure: ##STR13## The compound havingthe structure: ##STR14## of our invention is capable of augmenting orenhancing sweaty, cuminic aromas with castoreum-like under tones andsweaty, strong cuminic, cedar like aroma nuances on dryout.

The compound having the structure: ##STR15## may be prepared by methodswell known in the art, e.g., according to the reaction: ##STR16## andthis preparation is set forth in detail in Example I, infra.

Also contemplated within the scope of this invention are mixtures of the4-methyl-3-cyclohexene-1-carboxylic acid having the structure: ##STR17##with compounds which yield sweaty, animal, leathery notes definedaccording to the genera having the structures: ##STR18## wherein Rrepresents t-butyl or t-amyl as more particularly described in U.S. Pat.No. 3,702,343 issued on Nov. 7, 1972, the disclosure for which isincorporated by reference herein. In addition, the compound of ourinvention having the structure: ##STR19## is contemplated to be used inadmixture with the cedrol alkyl ethers disclosed in U.S. Pat. No.3,373,208 issued on Mar. 12, 1968 the disclosure of which isincorporated by reference herein. The cedrol alkyl ethers of U.S. Pat.No. 3,373,208 are defined according to the generic structure: ##STR20##wherein R represents methyl, ethyl, propyl, butyl, allyl or methallyl.

Contemplated within the scope of our invention are mole ratios of4-methyl-3-cyclohexene-1-carboxylic acid: 2-methyl-2-(t-alkylcyclohexyl) pentan-4-one:cedrol alkyl ethers of from 1:0:0 to 1:30:0 to1:1:30 to 1:30:1 to 1:30:0.

Specific 2-methyl-2(tertiary alkyl cyclohexyl) pentan-4-one contemplatedwithin the scope of our invention are those having the structures:##STR21## or those having the structures: ##STR22##

Taken alone the carboxylic acid derivative of our invention having thestructure: ##STR23## is useful as a cumin replacement and/or as a cuminaldehyde replacement. It is well known in the perfume industry thatcumin oil and cumin aldehyde have, under certain conditions, certainirritancy properties with respect to certain wearers.

The carboxylic acid having the structure: ##STR24## taken alone or takenfurther together with the pentanone derivatives defined according to thestructures: ##STR25## or with cedrol alkyl ether derivatives and one ormore auxiliary perfume ingredients including, for example, alcohols,aldehydes, ketones, terpenic hydrocarbons, nitriles, esters other thanthe esters of our invention, lactones, natural essential oils andsynthetic essential oils may be admixed so that the combined odors ofthe individual components produce a pleasant and desired fragrance,particularly and preferably in those fragrances where cumin oil or cuminaldehyde is necessary such as, cassie fragrances. Such perfumecompositions usually contain (a) the main note or the "bouquet" orfoundation stone of the composition; (b) modifiers which round off andaccompany the main notes; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaportation; and (d) top noteswhich are usually low boiling, fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesome total of the effect of each of the ingredients. Thus, thecarboxylic acid derivative having the structure: ##STR26## taken aloneor taken further together with the pentanone derivatives having thestructure: ##STR27## or the cedrol alkyl ethers can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of the carboxylic acid derivative having the structure:##STR28## taken alone or taken further together with the pentanonederivatives having the structures: ##STR29## and the cedrol alkyl etherderivatives which will be effective in perfume compositions as well asin perfumed articles (e.g., perfumed polymers, anionic, nonionic,cationic or zwitterionic detergents, soaps, fabric softenercompositions, fabric softener articles, bath oils and hair preparationsand shampoos) and colognes depends upon many factors including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% ofthe carboxylic acid derivative having the structure: ##STR30## takenalone or taken further together with the pentanone derivatives havingthe structures: ##STR31## and/or cedrol alkyl ether derivatives, or evenless (e.g., 0.005%) can be used to impart, augment or enhance sweaty,cuminic aromas with castoreum under tones with sweaty, cuminic and cedarlike top notes and, when the carboxylic acid derivative having thestructure: ##STR32## is taken together with the pentanone derivativehaving the structure: ##STR33## in proportions of from 1:99 up to 99:1,then additional sweaty and leathery and animal like notes are impartedthereto to soaps, cosmetics, anionic, cationic, nonionic, orzwitterionic detergents, fabric softener compositions, fabric softenerarticles, shampoos, bath preparations and perfumed polymers such asmicroporous polyacrylic resins or microporous polyethylenes ormicroporous polypropylenes with or without containing fillers such astalc and mica. The amount employed can range up to 70% of the fragrancecomponents and will depend on considerations of cost, nature of the endproduct, the effect desired on the finished product and the particularfragrance sought.

The carboxylic acid derivative having the structure: ##STR34## is useful(taken alone or taken together with other ingredients in perfumecompositions) as an olfactory component in detergents and soaps, spaceodorants and deodorants, perfumes, colognes, toilet water, bathpreparations such as creams, deodorants, hand lotions and sun screens;powders such as talcs, dusting powder, face powder and the like. Whenused as an olfactory component as little as 0.05% of the carboxylic acidderivatives having the structure: ##STR35## will suffice to impart anintense sweaty, cuminic aroma with castoreum under tones and sweaty,cuminic and cedar aromas on dry out. Generally no more than 6% of thecarboxylic acid derivative having the structure: ##STR36## based on theultimate end product perfumed article is required in the perfumedarticle composition.

In addition, the perfume composition of fragrance composition of ourinvention can contain a vehicle or carrier for the carboxylic acidderivative having the structure: ##STR37## taken alone or furthertogether with the pentanone derivative having the structure: ##STR38##and/or the cedrol alkyl ethers of our invention. The vehicle can be aliquid such as a non-toxic alcohol (e.g., ethyl alcohol), a non-toxicglycol (e.g., 1,2-propylene glycol) or the like. The carrier can also bean absorbent solid such as a gum (e.g., gum arabic or xanthan gum) orcomponents for encapsulating the composition (such as gelatin) as likecoacervation or components for encapsulating the composition by means ofpolymerization of a prepolymer such as the use of the ureaformaldehyderesin.

It will thus be apparent that the carboxylic acid derivative of ourinvention having the structure: ##STR39## taken alone or taken furthertogether with the pentanone derivatives having the structures: ##STR40##and/or the cedrol alkyl ether derivatives can be utilized to alter,modify or enhance sensory properties particularly organolepticproperties in a wide variety of consumable materials.

The following examples serve to illustrate our invention but ourinvention is only intended to be limited as indicated in the appendedclaims. All parts and percentages given herein are by weight unlessotherwise specified.

EXAMPLE I PREPARATION OF 4-METHYL-3-CYCLOHEXENE-1-CARBOXYLIC ACIDREACTION ##STR41## Into 1 liter reaction flask equipped with stirrer,thermometer reflux condenser and heating mantle is placed 100 mlanhydrous methyl 1.25 moles (100 grams) of 50% aqueous NaOH solution,100 ml water and 154 grams (1 mole) of the methyl ester of4-methyl-cyclohexene-1-carboxylic acid. The reaction mass is stirred fora period of 5 hours at room temperature and then extracted with 1 volumeof diethyl ether. The aqueous layer is set aside with 10% hydrochloricacid and extracted with diethyl ether. The diethyl ether extracts arewashed with saturated sodium chloride solution and the ether isevaporated yielding 100.5 grams of solid melting at 95° C. This materialis the carboxylic acid having the structure: ##STR42## as confirmed byNMR and IR analysis.

FIG. 1 sets forth the NMR spectrum for this compound.

FIG. 2 sets forth the IR spectrum for this compound.

The resulting compound has a sweaty cuminic aroma with castoreum undertones (fresh) and a sweaty cuminic cedar like aroma on dry out.

EXAMPLE II

    ______________________________________                                        CASSIE PERFUME COMPOSITION:                                                   Ingredient            Parts by Weight                                         ______________________________________                                        Linalool              40                                                      4-Methyl-3-cyclohexene-1-carboxylic                                           acid prepared according to Example I                                                                10                                                      Terpineol             150                                                     Methyl heptenyl carbonate                                                                           10                                                      Orris Concrete        20                                                      Methyl ionone         300                                                     Mimosa absolute       50                                                      Eugenol               100                                                     Anisic aldehyde       70                                                      Orange flower absolute                                                                              10                                                      Cassie absolute       10                                                      Methyl naphthyl ketone                                                                              50                                                      Hydroxy citronellal   150                                                     n-Decyl aldehyde                                                              (10% in diethyl phthalate)                                                                          10                                                      ______________________________________                                    

The 4-methyl-3-cyclohexene-1-carboxylic acid is an excellent replacerfor the cuminic aldehyde. In fact, the4-methyl-3-cyclohexene-1-carboxylic acid imparts a more "natural"character to this cassie fragrance formulation.

EXAMPLE III CHYPRE ESSENCE

The following Chypre essence composition is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Santalol              60                                                      Coumarin              70                                                      Musk ketone           30                                                      Musk ambrette         20                                                      Ambreine absolute     25                                                      Tarragon oil          25                                                      Angelica root oil     5                                                       Clary sage            30                                                      Vetivert oil          60                                                      Linalool              30                                                      Patchouli oil         20                                                      Iso-eugenol           35                                                      Methyl ionone         50                                                      Oakmoss absolute      60                                                      Bergamot oil          225                                                     Jasmin absolute       20                                                      Rose absolute         15                                                      Methyl salicylate     2                                                       Lavender oil          3                                                       Vanillin              15                                                      Heliotropin           35                                                      Ylang oil, Manila     70                                                      Cinnamyl acetate      25                                                      Benzoil resinoid      50                                                      2-methyl-2-(4'-t-butyl cyclohexyl)                                            pentan-4-one prepared according                                               to the process of Example II of                                               U.S. Pat. No. 3,702,343 incorporated                                          by reference herein)  20                                                      4-methyl-3-cyclohexene-1-                                                     carboxylic acid prepared according                                            to Example I, supra   20                                                      ______________________________________                                    

The original mixture without the 2-methyl-2-(4'-t-butyl cyclohexyl)pentan-4-one and without the 4-methyl-3-cyclohexene-1-carboxylic acidwas designed as a chypre essence. The addition of the pentan-4-onecompound taken together with the 4-methyl-3-cyclohexene-1-carboxylicacid and the quantities given increases (a) the intensity of theessence; (b) the diffusion of the fragrance; (c) adds certain "naturalsweaty, leathery, cuminic animal like cuminic cedar like and castoreumlike aroma nuances".

EXAMPLE IV

The following mixture is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Bergamot oil CP       100                                                     Orange oil Fla. CP    100                                                     Bitter orange oil WI  50                                                      Lemon oil Cal. CP     20                                                      Mandarin oil          20                                                      Lime oil exp. WI      10                                                      Ocimene               10                                                      Ortho tertiary butyl cyclohexanyl acetate                                                           10                                                      Cedryl methyl ether   50                                                      4-methyl-3-cyclohexene-1-carboxylic acid                                                            50                                                      ______________________________________                                    

The mixture of cedryl methyl ether and4-methyl-3-cyclohexene-1-carboxylic acid imparts to this woody amberfragrance an intense cedar, cumin like, castoreum like aroma nuance.When the pentanone derivative having the structure: ##STR43## is addedin the amount of 20 parts by weight to this mixture. The resultingmixture in addition, has pleasant animal, leathery and sweaty aromaunder tones.

EXAMPLE V PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table I below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table I below:

                  TABLE I                                                         ______________________________________                                        Substance        Aroma Description                                            ______________________________________                                        4-Methyl-3-cyclohexene-1-                                                                      Sweaty, cuminic aroma with                                   carboxylic acid  castoreum under tones (fresh)                                                 with sweaty, strong cuminic                                                   cedar like aroma nuances on                                                   dryout.                                                      The fragrance formulation                                                                      A strong cassie aroma with                                   of Example II.   cuminic sweaty notes and                                                      castoreum cedar like under-                                                   tones.                                                       The fragrance formulation                                                                      A chypre aroma with sweaty,                                  of Example III.  leathery, animal like cuminic                                                 like castoreum like and cedar                                                 wood undertones.                                             The fragrance formulation                                                                      A strong cedar aroma with                                    of Example IV.   intense woody, amber nuances                                                  and cuminic castoreum like                                                    undertones.                                                  ______________________________________                                    

EXAMPLE VI PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon April 6, 1976 incorporated by reference herein) with aroma nuances asset forth in Table I of Example V, are prepared containing 0.10%, 0.15%,0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table I ofExample V. They are prepared by adding and homogeneously mixing theappropriate quantity of substance set forth in Table I of Example V inthe liquid detergent. The detergents all possess excellent aromas as setforth in Table I of Example V, the intensity increasing with greaterconcentrations of substance as set forth in Table I of Example V.

EXAMPLE VII PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Compositions as set forth in Table I of Example V are incorporated intocolognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; andinto handkerchief perfumes at concentrations of 15%, 20%, 25% and 30%(in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table I of ExampleV are imparted to the colognes and to the handkerchief perfumes at alllevels indicated.

EXAMPLE VIII PREPARATION OF SOAP COMPOSITIONS

One hundred grams of soap chips [per sample] (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table I of Exaple V untilhomogenous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table I of Example V.

EXAMPLE IX PREPARATION OF SOLID DETERGENT COMPOSITIONS

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated by referenceherein):

    ______________________________________                                        Ingredient        Percent by Weight                                           ______________________________________                                        "Neodol ® 45-11 (a C.sub.14 -C.sub.15                                     alcohol ethoxylanted with                                                     11 moles of ethylene oxide)                                                                     12                                                          Sodium carbonate  55                                                          Sodium citrate    20                                                          Sodium sulfate, water                                                         brighteners       q.s.                                                        ______________________________________                                    

This detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table I of Example V. Each of thedetergent samples has an excellent aroma as indicated in Table I ofExample V.

EXAMPLE X

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as dried-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and ther perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table I of Example V.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table I of Example V, supra, consist of a substrate coating having aweight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table I of Example V isadmixed in each case with the outer casing mixture, thereby providing atotal aromatized outer coating weight ratio to substrate of about 0.5:1by weight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a dryer on operation thereof ineach case using said dryer-added fabric softener non-woven fabrics andthese aroma characteristics are described in Table I of Example V,supra.

EXAMPLE XI HAIR SPRAY FORMULATIONS

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, New York, in 91.62 grams of 95% food gradeethanol. 8.0 grams of the polymer is dissolved in the alcohol. Thefollowing ingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                            Dioctyl sebacate         0.05 weight percent                                  Benzyl alcohol           0.10 weight percent                                  Dow Corning 473 fluid                                                         (prepared by the Dow Corning                                                                           0.10 weight percent                                  Corporation)                                                                  Tween 20 surfactant                                                           (prepared by ICI America 0.03 weight percent                                  Corporation)                                                                  One of the perfumery sub-                                                     stances as set forth in                                                       Table I of Example V, supra                                                                            0.10 weight percent                              ______________________________________                                    

The perfuming substances as set forth in Table I of Example V add aromacharacteristics as set forth in Table I of Example V which are ratherintense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XII CONDITIONING SHAMPOOS

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "COMPOSITION A".

Gafquat® 755 N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, New York) (5.0 weight percent) is admixed with 0.1weight percent sodium sulfate and 1.4 weight percent polyethylene glycol6000 distearate produced by Armak Corporation. This material is"COMPOSITION B".

The resulting COMPOSITION A & COMPOSITION B are then mixed in a 50:50 wtratio of A:B and cooled to 45° C. and 0.3 wt percent of perfumingsubstance as set forth in Table I of Example V is added to the mixture.The resulting mixture is cooled to 40° C. and blending is carried outfor an additional one hour in each case. At the end of this blendingperiod, the resulting material has a pleasant fragrance as indicated inTable I of Example V.

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a solid or liquid anionic, cationic, nonionic or zwitterionicdetergent comprising the step of adding to a solid or liquid anionic,cationic, nonionic or zwitterionic detergent base, an aroma augmentingor enhancing quantity of 4-methyl-3-cyclohexene-1-carboxylic aciddefined according to the structure: ##STR44##